JP2010245064A - Method for manufacturing circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a circuit board, capable of giving a circuit board having good bondability between an insulating layer as an electric insulating layer and a metal layer as a conductor layer without executing roughening treatment of the surface of the insulating film or treatment using an acid aqueous solution. <P>SOLUTION: The method for manufacturing the circuit board includes the steps of irradiating the surface of an insulating film with an ultraviolet ray, the insulating film formed by curing a curable resin composition containing an alicyclic olefin polymer having a functional group and a curing agent, and forming a metal layer by an electroless plating method on the surface of the insulating film irradiated with the ultraviolet ray. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method of manufacturing a circuit board, and more particularly, to provide a circuit board having good adhesion between an insulating film and a metal layer without performing a roughening process on the surface of the insulating film or a treatment with an acidic aqueous solution. The present invention relates to a method of manufacturing a circuit board capable of performing

  With the pursuit of downsizing, multi-functionalization, high-speed communication, etc. of electronic devices, higher density of circuit boards used in electronic devices is required, and therefore circuit boards are being made multilayered. A multilayer circuit board is usually formed by laminating an electrical insulation layer on an inner layer substrate composed of an electrical insulation layer and a conductor layer formed on the surface, and forming a conductor layer on the electrical insulation layer. It is formed by repeatedly laminating an electrical insulating layer and forming a conductor layer thereon. When the conductor layer of such a multilayer circuit board has a high-density pattern, the insulating film used to form the electrical insulating layer is required to have good electrical characteristics such as a low dielectric constant and excellent adhesion. It is done. Conventionally, as a method for improving the adhesion between the electrical insulating layer and the conductor layer, a method of roughening the surface of the electrical insulating layer has been generally used. However, roughening the surface of the electrical insulating layer can cause problems such as transmission delay due to the skin effect in the high-frequency region. Therefore, the adhesion between the electrical insulating layer and the conductor layer can be reduced without roughening the surface of the electrical insulating layer. There is a need for technology to improve

  In response to such a demand, a technique for improving the adhesion between the electrical insulating layer having excellent electrical characteristics and the conductor layer has been studied. For example, Patent Document 1 discloses a laminate in which the surface of a cycloolefin polymer material having excellent electrical characteristics is subjected to ultraviolet irradiation treatment and plated, and thus the surface roughness remains small and the metal coating has good adhesion. Is disclosed. However, an electrical insulating layer made of a thermoplastic cycloolefin polymer material as described in Patent Document 1 can sufficiently support a conductor layer in a multilayer circuit board that can become high temperature due to heat generation caused by energization. There was a problem that I could not.

  In Patent Document 2, an uncured or semi-cured resin layer is formed using a curable resin composition containing an insulating polymer such as an alicyclic olefin polymer and a curing agent, and a resin layer A compound having a structure capable of coordinating with a metal is brought into contact with the surface and cured to form an electrical insulating layer, which is oxidized and then plated with an aqueous solution of permanganate. It is disclosed that an electrical insulating layer having excellent adhesion to a conductor layer can be obtained. However, the surface treatment by such a wet process has a problem that the management of the treatment liquid becomes complicated, and an oxidizing agent such as permanganate cannot be used in a large amount from the viewpoint of avoiding environmental load. There are restrictions such as.

  On the other hand, Patent Documents 3 to 5 describe that a resin layer such as polyphenylene ether is subjected to plasma treatment and ultraviolet irradiation to perform electroless plating. However, an electrical insulating layer made of polyphenylene ether has a problem that electrical characteristics are not sufficient.

JP 2008-94923 A JP 2003-158373 A JP 2003-338683 A JP 2007-084463 A JP 2008-244139 A

  The present invention provides a circuit board having good adhesion between an insulating film serving as an electrical insulating layer and a metal layer serving as a conductor layer without performing roughening treatment on the surface of the insulating film or treatment with an acidic aqueous solution. An object of the present invention is to provide a method for manufacturing a circuit board.

  As a result of diligent research to achieve the above object, the present inventor formed a metal layer on an insulating film obtained by curing a curable resin composition containing an alicyclic olefin polymer having a functional group and a curing agent. In doing so, the surface of the insulating film is irradiated with ultraviolet rays, and then a metal layer is formed on the surface by electroless plating, so that the insulating film can be processed without roughening the surface of the insulating film or treatment with an acidic aqueous solution. It has been found that a circuit board having good adhesion between the metal layer and the metal layer can be obtained. The present invention has been completed based on this finding.

  Thus, according to the present invention, the surface of the insulating film formed by curing the curable resin composition containing the alicyclic olefin polymer having a functional group and the curing agent is irradiated with ultraviolet rays, Next, a method of manufacturing a circuit board is provided, which includes a step of forming a metal layer on the surface of the insulating film irradiated with the ultraviolet rays by an electroless plating method.

  The above-described circuit board manufacturing method is preferably a method in which the surface of the insulating film is subjected to a dry process treatment before the surface is irradiated with ultraviolet rays.

  In the above circuit board manufacturing method, the dry process treatment is preferably plasma treatment or corona treatment.

  According to the present invention, it is possible to provide a circuit board having good adhesion between an insulating film serving as an electrical insulating layer and a metal layer serving as a conductor layer without performing roughening treatment on the surface of the insulating film or treatment with an acidic aqueous solution. A circuit board manufacturing method is obtained.

  The method for producing a circuit board according to the present invention irradiates the surface of an insulating film formed by curing a curable resin composition containing an alicyclic olefin polymer having a functional group and a curing agent with ultraviolet rays. Then, a step of forming a metal layer by an electroless plating method on the surface of the insulating film irradiated with the ultraviolet rays is included.

  The curable resin composition used for forming the insulating film used in the method for producing a circuit board of the present invention contains an alicyclic olefin polymer having a functional group and a curing agent. Here, the alicyclic olefin polymer having a functional group used in the present invention is a polymer having a repeating unit derived from an olefin having an alicyclic structure (alicyclic olefin) and having a functional group. is there.

  Examples of the alicyclic structure that can be contained in the alicyclic olefin polymer having a functional group used in the present invention include a cycloalkane structure and a cycloalkene structure. From the viewpoint of mechanical strength, heat resistance, and the like, A cycloalkane structure is preferable, and a norbornane structure is particularly preferable. Examples of the alicyclic structure include monocycles, polycycles, condensed polycycles, bridged rings, and polycycles formed by combining these. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15 in the mechanical strength, Various characteristics of heat resistance and moldability are highly balanced and suitable. In addition, the alicyclic olefin polymer having a functional group used in the present invention is usually thermoplastic.

  The ratio of the repeating unit derived from the alicyclic olefin in the alicyclic olefin polymer having a functional group is not particularly limited, but is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 70 to 100%. % By weight. When the ratio of the repeating unit derived from the alicyclic olefin is excessively small, the heat resistance is inferior, which is not preferable. The repeating unit other than the repeating unit derived from the alicyclic olefin is not particularly limited and is appropriately selected depending on the purpose.

  Although the functional group which the alicyclic olefin polymer which has a functional group has is not specifically limited, It is preferable that it is a functional group which can react with the functional group which the hardening | curing agent to use and can form a bond. Specific examples of functional groups possessed by the alicyclic olefin polymer include hydroxyl group, carboxyl group, alkoxyl group, epoxy group, glycidyl group, oxycarbonyl group, carbonyl group, amino group, ester group, carboxylic anhydride group, etc. In particular, a carboxyl group or a carboxylic anhydride group is preferable. In addition, the alicyclic olefin polymer having a functional group may have two or more kinds of functional groups. In addition, the functional group of the alicyclic olefin polymer may be directly bonded to an atom constituting the main chain of the polymer, but other divalent groups such as a methylene group, an oxy group, an oxycarbonyloxyalkylene group, and a phenylene group. It may be bonded via the group. The amount of the functional group in the alicyclic olefin polymer having a functional group is not particularly limited, but is usually 5 to 60 mol%, preferably based on the number of moles of all repeating units constituting the alicyclic olefin polymer. Is 10 to 50 mol%.

  In general, alicyclic olefin polymers are obtained by addition polymerization or ring-opening polymerization of alicyclic olefins, and hydrogenation of unsaturated bond portions as necessary, or addition polymerization or ring-opening polymerization of aromatic olefins. And hydrogenating the aromatic ring portion of the polymer. And the alicyclic olefin polymer which has a functional group used by this invention, for example, adds another monomer as needed and polymerizes the alicyclic olefin which has a functional group as needed. (2) By copolymerizing an alicyclic olefin having no functional group with a monomer having a functional group, (3) an aromatic olefin having a functional group may be converted to another monomer as required. (4) copolymerizing an aromatic olefin having no functional group with a monomer having a functional group, by hydrogenating the aromatic ring portion of the resulting polymer. By hydrogenating the aromatic ring portion of the polymer obtained by (5), or (5) introducing a functional group-containing compound into the alicyclic olefin polymer having no functional group, or (6) (1) above The functional group of the alicyclic olefin polymer having a functional group (for example, a carboxylic acid ester group) obtained as in (5) is converted into another functional group (for example, a carboxyl group) by, for example, hydrolysis. Can be obtained. In the present invention, the polymer obtained by the method (1) is particularly preferably used.

Specific examples of the cyclic olefin compound having a functional group that can be used as a monomer having a functional group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-hydroxy. Carbonylbicyclo [2.2.1] hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-hydroxycarbonyltetracyclo [6.2.1] ^.1,3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] dodeca-4-ene, 9-carboxymethyl-9-hydroxycarbonyl tetracyclo [6.2.1.1 ^{3, 6.} 0 ^2,7 ] dodec-4-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-exo-10-endo-dihydroxycarbonyltetracyclo [6. 2.1.1 ^3,6 . Cyclic olefins having a carboxyl group such as 0 ^2,7 ] dodec-4-ene; bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, tetracyclo [6.2.1 ^.1,3,6 . 0 ^2,7] dodeca-4-ene-9,10-dicarboxylic anhydride, hexacyclo [10.2.1.1 ^{3, 10.} 1 ^5,8 . 0 ^2,11 . Cyclic olefins having a carboxylic acid anhydride group such as 0 ^4,9 ] heptadeca-6-ene-13,14-dicarboxylic anhydride; 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.1 ^{3 , 6} . 0 ^2,7 ] dodec-4-ene, 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2 -Cyclic olefins having a carboxylic acid ester group such as ene; and the like. These may be used alone or in combination of two or more.

Specific examples of the alicyclic olefin having no functional group include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo [2.2.1] hept-2. -Ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] ] Hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene (common name: di) Cyclopentadiene), tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (common name: tetracyclododecene), 9-methyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] dodeca-4-ene, 9-methylidene - tetracyclo [6.2.1.1 ^{3, 6.} 0 ^2,7 ] dodec-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] dodeca-4-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8] tetradeca -3,5,7,12- tetraene, cyclopentene, etc. cyclopentadiene and the like, which may be used in combination of two or more may be used singly.

  Examples of aromatic olefins (having no functional group) include styrene, α-methylstyrene, divinylbenzene, and the like, and these may be used alone or in combination of two or more. .

  Examples of the monomer having a functional group other than the alicyclic olefin having a functional group that can be copolymerized with an alicyclic cycloolefin or an aromatic olefin include an ethylenically unsaturated compound having a functional group. Specific examples thereof include unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, α-ethylacrylic acid, 2-hydroxyethyl (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid; maleic anhydride, butenyl Unsaturated carboxylic acid anhydrides such as succinic anhydride, tetrahydrophthalic anhydride, citraconic anhydride; and the like. These may be used alone or in combination of two or more.

  Examples of the monomer having no functional group other than the alicyclic olefin that can be copolymerized with the alicyclic cycloolefin or the aromatic olefin include ethylenically unsaturated compounds having no functional group. Specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, and 4-methyl-1. -Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc., ethylene or α-olefin having 2 to 20 carbon atoms; 1,4- And the like; hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene nonconjugated dienes such. These may be used alone or in combination of two or more.

  The molecular weight of the cyclic olefin polymer used in the present invention is not particularly limited, but the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrohydrofuran as a solvent is in the range of 500 to 1,000,000. It is preferable that it is in the range of 1,000 to 500,000.

As a polymerization catalyst when the cyclic olefin polymer used in the present invention is obtained by a ring-opening polymerization method, a conventionally known metathesis polymerization catalyst can be used. Examples of the metathesis polymerization catalyst include transition metal compounds containing atoms such as Mo, W, Nb, Ta, and Ru. Among them, compounds containing Mo, W, or Ru are preferable because of high polymerization activity. Specific examples of particularly preferred metathesis polymerization catalysts include: (1) Molybdenum or tungsten compounds having a halogen group, an imide group, an alkoxy group, an allyloxy group, or a carbonyl group as a ligand as a main catalyst, and an organometallic compound. Examples thereof include a catalyst as a second component and (2) a metal carbene complex catalyst having Ru as a central metal. Examples of compounds used as the main catalyst in the catalyst (1) include halogenated molybdenum compounds such as MoCl ₅ and MoBr _5, and halogenated compounds such as WCl ₆ , WOCl ₄ , tungsten (phenylimide) tetrachloride, diethyl ether, and the like. A tungsten compound is mentioned. Examples of the organometallic compound used as the second component in the catalyst (1) include organometallic compounds of Group 1, Group 2, Group 12, Group 13 or Group 14 of the periodic table. Of these, organolithium compounds, organomagnesium compounds, organozinc compounds, organoaluminum compounds, and organotin compounds are preferred, and organolithium compounds, organoaluminum compounds, and organotin compounds are particularly preferred. Examples of the organic lithium compound include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, neophyllithium and the like. Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, allylmagnesium bromide, neopentylmagnesium chloride, neophyllmagnesium chloride and the like. Examples of the organic zinc compound include dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, ethylaluminum diethoxide, and the like. An aluminoxane compound obtained by a reaction between an organoaluminum compound and water can also be used. Examples of the organic tin compound include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin. The amount of these organometallic compounds added varies depending on the organometallic compound used, but is preferably 0.1 to 10,000 times, more preferably 0.2 to 5,000 times the center metal of the main catalyst. 0.5 to 2,000 times is particularly preferable. The metal carbene complex catalyst (2) having Ru as a central metal includes (1,3-dimesityl-imidazolidine-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, bis (tricyclohexylphosphine) benzylidene. Ruthenium dichloride, tricyclohexylphosphine- [1,3-bis (2,4,6-trimethylphenyl) -4,5-dibromoimidazol-2-ylidene]-[benzylidene] ruthenium dichloride, 4-acetoxybenzylidene (dichloro) ( 4,5-dibromo-1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium and the like.

  The ratio of the metathesis polymerization catalyst to the monomer is such that the molar ratio of (transition metal in the metathesis polymerization catalyst: monomer) is usually in the range of 1: 100 to 1: 2,000,000, preferably 1: It is in the range of 200 to 1: 1,000,000. If the amount of the catalyst is too large, it is difficult to remove the catalyst. If the amount is too small, sufficient polymerization activity cannot be obtained.

  The polymerization reaction is usually performed in an organic solvent. The organic solvent to be used is not particularly limited as long as the polymer is dissolved or dispersed under predetermined conditions and does not affect the polymerization, but industrially used one is preferable. Specific examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, and tricyclodecane. , Alicyclic hydrocarbons such as hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene and dichlorobenzene Halogenated aromatic hydrocarbons such as: Nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene, and acetonitrile; Diethyl ether, tetrahydrofuran, etc. Et - ether solvents; anisole, and the like aromatic ether solvents such as phenetole. Among these, industrially general-purpose aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ether solvents, and aromatic ether solvents are preferable.

  The amount of the solvent used is preferably such that the concentration of the monomer in the solution is 1 to 50% by weight, more preferably 2 to 45% by weight, and 3 to 40% by weight. It is particularly preferable that the amount is as follows. When the monomer concentration is 1% by weight or less, the productivity is poor, and when it is 50% by weight or more, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction becomes difficult.

  The polymerization reaction is initiated by mixing the monomer and the metathesis polymerization catalyst. As a method of mixing, the metathesis polymerization catalyst solution may be added to the monomer solution or vice versa. When the metathesis polymerization catalyst is a mixed catalyst comprising a transition metal compound as a main catalyst and an organometallic compound as a second component, the reaction solution of the mixed catalyst may be added to the monomer solution, and vice versa. But it ’s okay. Further, the transition metal compound solution may be added to the mixed solution of the monomer and the organometallic compound, or vice versa. Furthermore, the organometallic compound may be added to the mixed solution of the monomer and the transition metal compound, or vice versa.

  The polymerization temperature is not particularly limited, but is generally -30 ° C to 200 ° C, preferably 0 ° C to 180 ° C. The polymerization time is usually 1 minute to 100 hours, but is not particularly limited.

  Examples of a method for adjusting the molecular weight of the obtained cyclic olefin polymer include a method of adding an appropriate amount of a vinyl compound or a diene compound. The vinyl compound used for molecular weight adjustment is not particularly limited as long as it is an organic compound having a vinyl group, but α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrene, vinyltoluene and the like Styrenes; Ethers such as ethyl vinyl ether, i-butyl vinyl ether, and allyl glycidyl ether; Halogen-containing vinyl compounds such as allyl chloride; Oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol, and glycidyl methacrylate; Nitrogen-containing vinyl compounds such as acrylamide Can be mentioned. Diene compounds include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene, etc. Non-conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc. Can be mentioned. The amount of the vinyl compound or diene compound to be added can be arbitrarily selected from 0.1 to 10 mol% based on the monomer depending on the molecular weight to be obtained.

  As a polymerization catalyst when the cyclic olefin polymer used in the present invention is obtained by an addition polymerization method, for example, a catalyst comprising a titanium, zirconium or vanadium compound and an organoaluminum compound is preferably used. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst is a molar ratio of the metal compound to the monomer in the polymerization catalyst and is usually in the range of 1: 100 to 1: 2,000,000.

  When a hydrogenated ring-opening polymer is used as the cyclic olefin polymer used in the present invention, hydrogenation of the ring-opening polymer is usually carried out using a hydrogenation catalyst. The hydrogenation catalyst is not particularly limited, and a catalyst generally used for hydrogenation of an olefin compound may be appropriately employed. Specific examples of the hydrogenation catalyst include, for example, cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium. Ziegler catalyst comprising a combination of a transition metal compound and an alkali metal compound; dichlorotris (triphenylphosphine) rhodium, JP-A-7-2929, JP-A-7-149823, JP-A-11-209460, JP-A-11-158256, Ruthenium compounds such as bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride described in Kaihei 11-193323, JP-A-11-209460, etc. Of a noble metal complex catalyst; include homogeneous catalysts such as. Also, heterogeneous catalysts in which a metal such as nickel, palladium, platinum, rhodium, ruthenium is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide, such as nickel / silica, nickel / diatomaceous earth, nickel / Alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, and the like can also be used. It is also possible to use the metathesis polymerization catalyst as it is as a hydrogenation catalyst.

  The hydrogenation reaction is usually performed in an organic solvent. The organic solvent can be appropriately selected depending on the solubility of the produced hydrogenated product, and the same organic solvent as the polymerization solvent can be used. Therefore, after the polymerization reaction, the hydrogenation catalyst can be added and reacted without changing the solvent. Furthermore, among the above polymerization solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ether solvents, aromatic ether solvents are preferred because they do not react in the hydrogenation reaction. Ether solvents are particularly preferred, and tetrahydrofuran is most preferred.

  The hydrogenation reaction conditions may be appropriately selected according to the type of hydrogenation catalyst used. The reaction temperature is usually -20 to 250 ° C, preferably -10 to 220 ° C, more preferably 0 to 200 ° C. If it is less than −20 ° C., the reaction rate is slow, and if it exceeds 250 ° C., side reactions tend to occur. The pressure of hydrogen is usually 0.01 to 10.0 MPa, preferably 0.05 to 8.0 MPa. When the hydrogen pressure is less than 0.01 MPa, the hydrogen addition rate is slow, and when it exceeds 10.0 MPa, a high pressure reactor is required.

  The time for the hydrogenation reaction is appropriately selected in order to control the hydrogenation rate. The reaction time is usually in the range of 0.1 to 50 hours, and 50% or more, preferably 70% or more, more preferably 80% or more, most preferably, of the carbon-carbon double bonds of the main chain in the polymer. 90% or more can be hydrogenated.

  The catalyst used for the reaction may be removed. The removal method is not particularly limited, and examples thereof include methods such as centrifugation and filtration. Furthermore, the catalyst removal can be promoted by adding a catalyst deactivator such as water or alcohol, or by adding an adsorbent such as activated clay, alumina, or silicon earth.

  The curing agent used in the present invention is not particularly limited as long as it forms a cross-linked structure on the alicyclic olefin polymer having a functional group by heating, and it is not limited to a general curable resin composition for forming an electric insulating film. Although the compounding hardening | curing agent can be used, the compound which has two or more functional groups which can react with the functional group of the alicyclic olefin polymer which has a functional group to be used, and can form a bond is used as a hardening | curing agent. It is preferable. For example, as an alicyclic olefin polymer having a carboxyl group or a carboxylic acid anhydride group as the alicyclic olefin polymer having a functional group, the curing agent preferably used includes a polyvalent epoxy compound, a polyvalent olefin polymer Examples include isocyanate compounds, polyvalent amine compounds, polyhydric hydrazide compounds, aziridine compounds, basic metal oxides, and organometallic halides. These may be used alone or in combination of two or more. May be. These compounds and peroxides may be used in combination as a curing agent.

  Examples of the polyvalent epoxy compound that can be used as a curing agent include a phenol novolac epoxy compound, a cresol novolac epoxy compound, a cresol epoxy compound, a bisphenol A epoxy compound, a bisphenol F epoxy compound, and a hydrogenated bisphenol A epoxy. Glycidyl ether type epoxy compounds such as compounds; polycyclic epoxy compounds such as alicyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, isocyanurate type epoxy compounds, phosphorus-containing epoxy compounds; The compound which has the above epoxy groups is mentioned, These may be used individually by 1 type and may use 2 or more types together.

  As the polyvalent isocyanate compound that can be used as a curing agent, diisocyanates and triisocyanates having 6 to 24 carbon atoms are preferable. Examples of diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, etc. Is mentioned. Examples of triisocyanates include 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, etc., and these are used alone. It may also be used in combination of two or more.

  Examples of the polyvalent amine compound that can be used as a curing agent include aliphatic polyamine compounds having 4 to 30 carbon atoms having two or more amino groups, and aromatic polyamine compounds, such as guanidine compounds. Those having non-conjugated nitrogen-carbon double bonds are not included. Examples of the aliphatic polyvalent amine compound include hexamethylene diamine, N, N′-dicinnamylidene-1,6-hexane diamine, and the like. Examples of aromatic polyvalent amine compounds include 4,4′-methylenedianiline, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4 ′-(m-phenylenediisopropylidene) dianiline, 4,4 ′-( p-phenylenediisopropylidene) dianiline, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 1,3,5-benzenetriamine, and the like. These may be used alone. Or two or more of them may be used in combination.

  Examples of polyhydric hydrazide compounds that can be used as curing agents include isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, maleic acid dihydrazide, itaconic acid dihydrazide, trimellitic acid dihydrazide, 1,3,5 -Benzenetricarboxylic acid dihydrazide, pyromellitic acid dihydrazide, etc. are mentioned, These may be used individually by 1 type and may use 2 or more types together.

  Examples of aziridine compounds that can be used as the curing agent include tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, tris [1- (2-methyl) aziridinyl] phosphinoxide, hexa [1- (2-Methyl) aziridinyl] triphosphatriazine and the like may be mentioned, and these may be used alone or in combination of two or more.

  In the case of using an alicyclic olefin polymer having a carboxyl group or a carboxylic anhydride group as the alicyclic olefin polymer having a functional group, the reactivity with the functional group is moderate among the aforementioned curing agents. From the viewpoint of easy handling of the curable resin composition, polyvalent epoxy compounds are preferably used, and glycidyl ether type epoxy compounds and alicyclic polyvalent epoxy compounds are particularly preferably used.

  The amount of the curing agent used in the curable resin composition is usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 100 parts by weight of the alicyclic olefin polymer having a functional group. The range is 50 parts by weight. By using a hardening | curing agent with the usage-amount of such a range, the mechanical strength and electrical property of the hardened | cured material obtained by hardening | curing curable resin composition will become favorable.

  In order to accelerate the curing of the curable resin composition, the curable resin composition may contain a curing accelerator or a curing aid. As the curing accelerator, a curing accelerator blended in a general curable resin composition for forming an electrical insulating film may be used. When a polyvalent epoxy compound is used as the curing agent, a tertiary amine type is used. A compound, a boron trifluoride complex compound, or the like is preferably used as the curing accelerator. Especially, when a tertiary amine compound is used, the insulation resistance, heat resistance, and chemical resistance of the resulting insulating film are improved.

  Specific examples of the tertiary amine compound include, for example, chain tertiary amine compounds such as benzyldimethylamine, triethanolamine, triethylamine, tributylamine, tribenzylamine, dimethylformamide; pyrazoles, pyridines, pyrazines , Pyrimidines, indazoles, quinolines, isoquinolines, imidazoles, triazoles and the like. Among these, imidazoles, particularly substituted imidazole compounds having a substituent are preferable.

  Specific examples of the substituted imidazole compound include, for example, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, Alkyl-substituted imidazole compounds such as 2,4-dimethylimidazole and 2-heptadecylimidazole; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole 1-benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2′-cyanoethyl) imidazole, 2-ethyl-4-methyl-1- [2 ′-(3 ″, 5 "-Diaminotriazinyl) ethyl] imidazo Like imidazole compounds substituted with a hydrocarbon group containing a ring structure, such as an aryl group or an aralkyl group such as. Among these, imidazole having a substituent containing a ring structure is preferable from the viewpoint of compatibility with an alicyclic olefin polymer having a functional group, and 1-benzyl-2-phenylimidazole is particularly preferable.

  These curing accelerators can be used alone or in combination of two or more. The blending amount of the curing accelerator may be appropriately selected depending on the purpose of use, but is usually 0.001 to 30 parts by weight, preferably 0. 0 to 100 parts by weight of the alicyclic olefin polymer having a functional group. It is 01-10 weight part, More preferably, it is 0.03-5 weight part.

  As the curing aid, a curing aid blended in a general curable resin composition for forming an electric insulating film may be used. Specific examples thereof include quinone dioxime, benzoquinone dioxime, and p-nitrosophenol. Oxime / nitroso curing aids such as: N, Nm-phenylene bismaleimide and other maleimide curing aids; diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and other allyl curing aids; ethylene glycol di Examples thereof include methacrylate-based curing aids such as methacrylate and trimethylolpropane trimethacrylate; vinyl-based curing aids such as vinyltoluene, ethylvinylbenzene, and divinylbenzene. These curing aids can be used alone or in combination of two or more, and the blending ratio thereof is usually 1 to 1000 parts by weight, preferably 10 to 500 parts per 100 parts by weight of the curing agent used. The range is parts by weight.

If necessary, the curable resin composition may contain a rubbery polymer and other thermoplastic resins (other than those described above). The rubbery polymer is a polymer having a glass transition temperature of room temperature (25 ° C.) or lower, and includes a normal rubbery polymer and a thermoplastic elastomer. By adding a rubbery polymer or a thermoplastic resin to the curable resin composition, the flexibility of the resulting multilayer printed circuit board film can be improved. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the rubbery polymer to be used may be appropriately selected, but is usually 5 to 200. Specific examples of rubber-like polymers include ethylene-α-olefin rubber-like polymers; ethylene-α-olefin-polyene copolymer rubbers; ethylene and unsaturated carboxylic acids such as ethylene-methyl methacrylate and etherene-butyl acrylate. Copolymers with esters; copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; alkyl acrylates such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate Polybutadiene, polyisoprene, styrene-butadiene or styrene-isoprene random copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer, pig Diene rubber such as diene- (meth) acrylic acid alkyl ester-acrylonitrile copolymer, butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymer; modified diene rubber such as epoxidized polybutadiene; butylene-isoprene A copolymer etc. are mentioned. Specific examples of the thermoplastic elastomer include aromatic vinyl such as styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, etc. Examples thereof include a conjugated diene block copolymer, a low crystalline polybutadiene resin, an ethylene-propylene elastomer, a styrene-grafted ethylene-propylene elastomer, a thermoplastic polyester elastomer, and an ethylene ionomer resin. Of these thermoplastic elastomers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, and the like are preferable. Specifically, JP-A-2-133406 and JP-A-2 Examples described in JP-A-3-305814, JP-A-3-72512, JP-A-3-74409, and the like.

  Examples of other thermoplastic resins that can be blended in the curable resin composition include, for example, low density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density polyethylene, ethylene-ethyl acrylate copolymer, ethylene-acetic acid. Examples include vinyl copolymer, polystyrene, polyphenylene sulfide, polyphenylene ether, polyamide, polyester, polycarbonate, and cellulose triacetate.

  The rubber-like polymer and other thermoplastic resins can be used alone or in combination of two or more, and the blending amount is appropriately selected within a range not impairing the object of the present invention. In order not to impair the properties of the circuit board film as an insulating material, the blending amount is preferably 30 parts by weight or less with respect to 100 parts by weight of the alicyclic olefin polymer having a functional group.

  For the purpose of improving the flame retardancy of the insulating film, the curable resin composition used in the present invention is, for example, curable for forming a general electric insulating film such as a halogen flame retardant or a phosphate ester flame retardant. You may mix | blend the flame retardant mix | blended with a resin composition. When the flame retardant is blended with the curable resin composition, the blending amount is preferably 100 parts by weight or less and more preferably 60 parts by weight or less with respect to 100 parts by weight of the alicyclic olefin polymer. .

  The curable resin composition used in the present invention may further include an inorganic filler, a flame retardant aid, a heat resistance stabilizer, a weather resistance stabilizer, an anti-aging agent, an ultraviolet absorber (laser processability improver) as necessary. Optional ingredients such as leveling agents, antistatic agents, slip agents, anti-blocking agents, anti-fogging agents, lubricants, dyes, natural oils, synthetic oils, waxes, emulsions, magnetic substances, dielectric property modifiers, toughening agents, etc. The What is necessary is just to select suitably the mixture ratio of an arbitrary component in the range which does not impair the objective of this invention.

  In the method for producing a circuit board of the present invention, an insulating film formed by curing the curable resin composition as described above is used. The insulating film used in the present invention may be composed of only the curable resin composition containing the alicyclic olefin polymer as described above, but at least the surface on which the metal layer is formed has a curable resin composition. What is necessary is just to harden a thing, and the composite_body | complex with another material may be sufficient. Among such composites, a two-layer structure of a layer formed by curing a curable resin composition containing an alicyclic olefin polymer / a layer (base material) made of another electrically insulating material. A layer formed by curing a curable resin composition containing an insulating film or an alicyclic olefin polymer / other electrically insulating material (base material) / curability containing an alicyclic olefin polymer An insulating film having a three-layer structure formed by curing the resin composition is preferably used.

  The insulating film used in the circuit board manufacturing method of the present invention is not limited to this, but is usually formed on an inner layer substrate having a conductive circuit on the surface. Specific examples of the inner layer substrate include an epoxy resin reinforced with glass fiber and a printed wiring board formed of BT resin. The thickness of the inner layer substrate is usually 50 μm to 2 mm, preferably 60 μm to 1.6 mm, more preferably 100 μm to 1 mm.

  As a method of forming an insulating film on the inner layer substrate, the above-mentioned curable resin composition is used as a solution or dispersion (these are also referred to as varnishes), applied to the inner layer substrate, and then the solvent is removed and dried. A method is generally employed in which a coating layer of a curable composition is formed and then the composition is cured. However, in the present invention, the curable resin composition is formed into a film (or sheet), and is superposed on the base material as necessary to form a composite, which is superposed on the inner substrate by thermocompression bonding or the like. After that, it is preferable to form the insulating film by curing the layer of the curable resin composition.

  The method for forming the curable resin composition into a film is not particularly limited, but in the present invention, it is preferably formed by a solution cast method or a melt cast method. In the solution casting method, after the solution or dispersion of the curable resin composition is applied to a support, the solvent is removed by drying.

  The organic solvent used to dissolve or disperse the curable resin composition of the present invention has a boiling point of preferably 30 to 250 ° C., more preferably 50 to 200 ° C. for convenience of volatilization by heating later. is there. Examples of such organic solvents include aromatic hydrocarbons such as toluene, xylene, ethylbenzene and trimethylbenzene; aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane; alicyclics such as cyclopentane and cyclohexane Hydrocarbons; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene; ether compounds such as anisole; methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. These solvents can be used alone or in combination of two or more.

  Among these solvents, non-polar solvents such as aromatic hydrocarbon solvents and alicyclic hydrocarbon solvents, and polar solvents such as ketone solvents are excellent as they can be embedded in fine wiring and do not generate bubbles. A mixed solvent obtained by mixing a solvent is preferable. Although the mixing ratio of these nonpolar solvents and polar solvents can be selected as appropriate, the weight ratio is usually 5:95 to 95: 5, preferably 10:90 to 90:10, more preferably 20:80 to 80:20. Range.

  The amount of the solvent used is appropriately selected according to the purpose of use, but the solid content concentration of the solution or dispersion of the curable resin composition is usually 5 to 70% by weight, preferably 10 to 65% by weight, more preferably. Is in the range of 15-60% by weight.

  There is no particular limitation on the method of dispersing or dissolving the curable resin composition in the solvent. For example, each component constituting the curable resin composition and the organic solvent may be mixed according to a conventional method, for example, magnetic Mixing can be performed using a stirrer, a high-speed homogenizer, a dispersion, a planetary stirrer, a twin-screw stirrer, a ball mill, a triple roll, or the like. The mixing temperature is preferably not higher than the temperature at which the reaction between the alicyclic olefin polymer having a functional group and the curing agent occurs and not higher than the boiling point of the organic solvent.

  Next, after the prepared varnish is usually impregnated and / or coated on a base material or coated on a support, the organic solvent constituting the varnish is removed by drying, whereby a layer of a curable resin composition is formed. Is obtained (solution casting method). Usually, the obtained film is laminated on the inner layer substrate, the support is peeled off as necessary, and then the curable resin composition layer of the film is cured to form an insulating film on the inner layer substrate. Then, a circuit board is obtained. This insulating film functions as an electrical insulating layer of the circuit board, and a conductor layer can be further formed thereon to make the circuit board multilayer. At this time, the insulating film formed on the inner layer substrate becomes a so-called interlayer insulating layer.

  Specific examples of the substrate used for impregnating and / or applying the varnish of the curable resin composition include a nonwoven fabric, a woven fabric, and a resin film. In addition, examples of the organic polymer as the material include polyacrylate, aramid, fluorine-containing aramid, liquid crystal polymer, polyethylene terephthalate, polycarbonate, polypropylene, polyethylene, polyethylene naphthalate, polyimide, nylon, etc., especially aramid, fluorine-containing Aramid and liquid crystal polymers are preferred from the viewpoints of flame retardancy and electrical properties. The substrate is a molded body that can be impregnated or coated with the varnish described above, and the film thickness is usually 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less, and usually 0.05 μm or more, preferably Is 0.1 μm or more. These base materials preferably have a linear expansion coefficient of 10 ppm / K or less.

  Examples of the nonwoven fabric include an aramid nonwoven fabric, a fluorine-containing aramid woven fabric, a liquid crystal polymer nonwoven fabric, a polyethylene terephthalate nonwoven fabric, a polycarbonate nonwoven fabric, and a nylon nonwoven fabric. Among these nonwoven fabrics, an aramid nonwoven fabric and a liquid crystal polymer nonwoven fabric are preferable. Examples of the woven fabric include aramid woven fabric, liquid crystal polymer woven fabric, polyethylene terephthalate woven fabric, polycarbonate woven fabric, and nylon woven fabric. Among these woven fabrics, an aramid woven fabric, a fluorine-containing aramid woven fabric, and a liquid crystal polymer woven fabric are preferable. As the resin film, polyamide film, aramid film, fluorine-containing aramid film, liquid crystal polymer film, polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, polyimide film, fluorinated polyimide film, A nylon film etc. are mentioned. Of these resin films, a polyimide film, a fluorinated polyimide film, an aramid film, a fluorinated aramid film, and a liquid crystal polymer film are preferable from the viewpoint of heat resistance, chemical resistance, linear expansion coefficient, and the like.

  The resin film that can be used as the support is usually a thermoplastic resin film, specifically, a polyethylene terephthalate film, a polypropylene film, a polyethylene film, a polycarbonate film, a polyethylene naphthalate film, a polyarylate film, and a nylon film; Etc. Among these resin films, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable from the viewpoints of heat resistance, chemical resistance, peelability after lamination, and the like. Examples of the metal foil that can be used as the support include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil. From the viewpoint of good conductivity, a copper foil, particularly an electrolytic copper foil or a rolled copper foil is preferred. The thickness of the support is not particularly limited, but is usually 1 to 200 μm, preferably 2 to 150 μm, more preferably 3 to 100 μm from the viewpoint of workability and the like.

  Examples of the method of impregnating and / or applying the resin composition varnish to the substrate or the method of applying the resin composition varnish to the support include methods such as immersion, roll coating, curtain coating, die coating, and slit coating. It is done.

  Drying conditions for removing the organic solvent are appropriately selected depending on the type of the organic solvent. The heating temperature is usually 30 to 200 ° C., preferably 40 to 180 ° C., and the heating time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

  The thickness of the film obtained as described above is usually 0.1 to 150 μm, preferably 0.5 to 100 μm, more preferably 1.0 to 80 μm.

  When an insulating film is formed on the inner layer substrate using the film including the layer of the curable resin composition as described above, the film is overlapped so as to be in contact with the conductor layer of the inner layer substrate, a pressure laminator, Use a press, vacuum laminator, vacuum press, roll laminator, or other pressurizer (laminate) so that there is substantially no void at the interface between the conductor layer on the inner substrate surface and the resin molding layer. The method of combining is mentioned. This thermocompression bonding is preferably performed under vacuum in order to improve the embedding property of the wiring pattern and suppress the generation of bubbles. The temperature of the thermocompression bonding operation is usually 30 to 250 ° C., preferably 70 to 200 ° C., the applied pressure is usually 10 kPa to 20 MPa, preferably 100 kPa to 10 MPa, and the time is usually 30 seconds to 5 hours, preferably Is 1 minute to 3 hours. The atmospheric pressure is usually 100 kPa to 1 Pa, preferably 40 kPa to 10 Pa under reduced pressure.

  In order to obtain the insulating film used in the present invention, for example, a film made of the above-described curable resin composition formed as described above may be cured, and curing of the curable resin composition is usually curable. This is done by heating the resin composition. The conditions for curing are appropriately selected according to the type of curing agent, but the temperature is usually 30 to 400 ° C., preferably 70 to 300 ° C., more preferably 100 to 200 ° C., and the time is usually 0.1. -5 hours, preferably 0.5-3 hours. The heating method is not particularly limited, and may be performed using, for example, an electric oven.

  Further, for the purpose of improving the flatness of the insulating film or increasing the thickness of the insulating film, two or more films containing a layer of the curable resin composition may be in contact with each other to form the insulating film.

  The method for producing a circuit board according to the present invention includes an insulating film formed by curing a curable resin composition containing a functional group-containing alicyclic olefin polymer and a curing agent. This is one of the characteristics that can be used. This insulating film has very low water absorption, low dielectric constant, and excellent electrical characteristics. Therefore, the circuit board obtained by the present invention has low signal transmission loss and excellent reliability such as migration resistance. It will be a thing.

  In the method for producing a circuit board according to the present invention, the surface of the insulating film obtained as described above is irradiated with ultraviolet rays, and then a metal layer is formed on the surface of the insulating film irradiated with the ultraviolet rays by an electroless plating method. Thus, a circuit board is obtained.

Irradiation of ultraviolet rays onto the surface of the insulating film performed in the present invention may be performed by irradiating the surface of the insulating film with ultraviolet rays having a wavelength of, for example, 100 to 400 nm, preferably 180 to 400 nm. Here, the atmosphere of the ultraviolet irradiation may be an atmosphere in which oxygen exists, such as in the air, or an atmosphere in which oxygen does not exist by filling with an inert gas (for example, nitrogen). From the viewpoint of obtaining a circuit board that is more excellent in adhesion to the substrate, an atmosphere in which oxygen exists, such as in the air, is preferable. Although the intensity | strength of the ultraviolet-ray to irradiate is not specifically limited, It is preferable that it is 1-500 mw / cm < ² >. Also, the irradiation time of ultraviolet rays is not particularly limited, but is usually in the range of 10 seconds to 30 minutes, and further, the distance between the surface of the insulating film and the ultraviolet light source is not particularly limited, and is usually set in the range of 100 μm to 30 cm. do it. In the circuit board manufacturing method of the present invention, the adhesion between the insulating film and the metal layer is good by irradiating the surface of the insulating film before forming the metal layer by the electroless plating method in this way. A circuit board is obtained.

  In the method for producing a circuit board according to the present invention, it is preferable to subject the surface of the insulating film to a dry process treatment before and after the ultraviolet irradiation to the surface of the insulating film as described above, and preferably before the ultraviolet irradiation. This dry process treatment is a treatment for modifying the surface of the insulating film without bringing the liquid into contact with the surface of the insulating film, and is a treatment other than the ultraviolet irradiation. Specific examples of this dry process treatment include plasma treatment (atmospheric pressure plasma treatment, low pressure plasma treatment, flame plasma treatment), corona treatment, and electron beam irradiation treatment. Among these, adhesion between the insulating film and the metal layer is included. From the viewpoint of improving the properties, particularly the adhesion under humidified conditions, plasma treatment and corona treatment are preferred.

  Atmospheric pressure plasma treatment that can be adopted as a dry process treatment is a method in which a single or mixed gas such as argon, helium, krypton, neon, xenon, hydrogen, nitrogen, and air is electronically excited with a plasma jet under atmospheric pressure. This is done by spraying an excited inert gas on the surface of the insulating film. Specifically, an excitation inert gas is usually generated by applying an AC voltage of 3 to 5 kHz and 2 to 3000 V between the electrodes.

  The low-pressure plasma treatment that can be employed as the dry process treatment is a simple substance or a mixed gas such as argon, helium, krypton, neon, xenon, hydrogen, nitrogen, air, etc. at an output of 200 to 1000 W under reduced pressure (usually 0.1 to 5 Torr). Is excited electronically with a plasma jet, and then charged particles are removed and an electrically neutral excited inert gas is sprayed onto the surface of the insulating film.

  Flame plasma treatment that can be employed as a dry process treatment is performed by blowing an ionized plasma flame in a flame generated when natural gas, propane gas, or the like is burned onto the surface of the insulating film.

The corona treatment that can be adopted as the dry process treatment is a treatment in which the surface of the insulating film is subjected to a corona discharge treatment. The corona treatment is performed, for example, by using a known corona discharge treatment machine and passing the substrate under the generated corona atmosphere. Here, the atmosphere of the corona treatment may be in the air, or may be an atmosphere adjusted with an inert gas (for example, nitrogen). Conditions of the corona treatment is usually 10 W · min / ^{m 2} or more, preferably a 30～300W · min / ^{m 2.}

  The electron beam irradiation treatment is performed by irradiating the surface of the insulating film with an electron beam generated by an electron beam accelerator. The atmosphere of the electron beam irradiation treatment may be in the air, or may be an atmosphere adjusted with an inert gas (for example, nitrogen) or the like.

  In the method for producing a circuit board of the present invention, the surface of the insulating film may be degreased with an aqueous sodium hydroxide solution or the like before, preferably, before or after the ultraviolet irradiation or dry process treatment on the surface of the insulating film. . Similarly, water washing treatment may be performed as appropriate.

  The surface of the insulating film before forming the metal layer obtained as described above is preferably not subjected to roughening treatment from the viewpoint of preventing transmission delay due to the skin effect in the high frequency region of the circuit board. The surface roughness (arithmetic mean roughness Ra) of the insulating film before forming the metal layer is preferably less than 0.3 μm, more preferably 0.2 to 0.01 μm.

  In the circuit board manufacturing method of the present invention, a metal layer is formed by electroless plating on the surface of the insulating film irradiated with at least ultraviolet rays obtained as described above. The material of the metal layer is not particularly limited as long as it is a metal material having conductivity, and a material generally used as a circuit forming material can be used. Suitable materials include metal materials such as copper, silver, gold, nickel, aluminum, and tungsten, and copper is particularly preferably used.

  In the electroless plating method, usually, catalyst nuclei such as silver, palladium, zinc, cobalt, gold, platinum, iridium, ruthenium, and osmium acting as a reduction catalyst are adsorbed on the surface of the insulating film. Next, a metal layer can be formed by bringing an electroless plating solution into contact with the surface of the insulating film on which the catalyst nuclei are adsorbed. As the electroless plating solution used in the electroless plating method, for example, a known autocatalytic electroless plating solution may be used. Metal species, reducing agent species, complexing agent species, hydrogen ion concentration contained in the plating solution The dissolved oxygen concentration and the like may be selected as appropriate. Examples of electroless plating solutions include electroless copper plating solutions containing ammonium hypophosphite or hypophosphorous acid, ammonium borohydride, hydrazine, formalin, etc. as reducing agents, and sodium hypophosphite as reducing agents. Electroless nickel-phosphorous plating solution, electroless nickel-boron plating solution using dimethylamine borane as reducing agent, electroless palladium plating solution, electroless palladium-phosphorous plating solution using sodium hypophosphite as reducing agent, electroless Examples thereof include a gold plating solution, an electroless silver plating solution, and an electroless nickel-cobalt-phosphorus plating solution using sodium hypophosphite as a reducing agent. In addition, it is preferable to perform the rust prevention process of making the metal layer formed by the electroless-plating method contact a rust preventive agent.

  In forming the metal layer on the surface of the insulating film, it is preferable to grow the metal layer by applying the electrolytic plating method on the metal layer formed by the electroless plating method. As the electrolytic plating solution used in this case, a known electrolytic plating solution may be used. For example, a copper sulfate plating solution, a copper pyrophosphate plating solution, an electrolytic nickel plating solution, or the like can be used. In addition, the electrolytic plating solution may contain additives such as a complexing agent, a brightening agent, a stabilizer, and a buffering agent as necessary.

The circuit board manufacturing method of the present invention includes the step of obtaining an insulating film having a metal layer formed on the surface as described above. The circuit board obtained in this manner is excellent in electrical characteristics and adhesion between the insulating film and the metal layer even without a roughening treatment with an oxidizing aqueous solution such as an aqueous solution of permanganate.

  In the method of using a metal layer formed on an insulating film as a conductive circuit, a conductive material layer is formed on the entire surface in a range where the conductive circuit is to be formed, and then a conductive pattern unnecessary for forming a circuit pattern. The method is roughly divided into a method for removing the material (subtractive method) and a method for forming a conductive material layer so as to have a circuit pattern (additive method). In the present invention, either method is adopted. Can do.

  As an example of applying the subtractive method, a metal layer is formed on the entire surface of the insulating film by the above-described method, and then an etching resist solution is applied to a portion of the metal layer to be left as a circuit pattern to form a resist film After the formation, an unnecessary conductive material is removed by immersion in an etching solution, and then the resist film is peeled off. In addition, as an example of applying the additive method, a resist film is formed by applying a resist solution to a portion where a metal layer is not necessary for forming a circuit pattern of an insulating film, and then a resist film is partially formed. A method of forming a metal layer on the insulating film by the above-described method and then peeling the resist film can be used.

  As described above, the circuit board (multilayer circuit board) obtained by the method for manufacturing a circuit board of the present invention may be one in which an insulating film and a metal layer are formed only on one side of the inner layer board. An insulating film and a metal layer may be formed on both sides. Further, an insulating film and a metal layer may be further formed on the insulating film and the metal layer formed on the inner layer substrate.

  The use of the circuit board obtained by the present invention is not particularly limited. For example, the circuit board can be suitably used as a substrate for a semiconductor element such as a CPU or a memory or other mounting component in an electronic device such as a computer or a mobile phone.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, unless otherwise indicated, the part and% in each example are a basis of weight.

Various physical properties were evaluated according to the following methods.
(1) Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer: measured by gel permeation chromatography (GPC) using toluene or tetrahydrofuran as a developing solvent, It calculated | required as a polystyrene conversion value.
(2) Hydrogenation rate of polymer: The hydrogenation rate means the ratio of the number of moles of unsaturated bonds hydrogenated to the number of moles of unsaturated bonds in the polymer before hydrogenation, and a ¹ H-NMR spectrum. Obtained by measurement.
(3) Carboxylic anhydride group content of polymer: The ratio of the number of moles of carboxylic anhydride groups to the total number of monomer units in the polymer, and was determined by ¹ H-NMR spectrum measurement.
(4) Thickness of each layer constituting the film: After cutting the insulating film before curing the layer formed by the curable resin composition and polishing the cross section, the cross section was observed with an optical microscope. It was measured.
(5) Surface roughness of the insulating film (arithmetic average roughness Ra): The surface roughness (arithmetic average roughness) of the surface of the sample (laminate) was measured using a surface shape measuring device (NT-1100: manufactured by WYKO). Ra) was measured.
(6) Adhesiveness between insulating film and metal layer: The peel strength between the insulating film and the copper plating layer in the sample (laminate) was measured according to JIS C6481-1996. Judged by criteria.
A: The average peel strength is 8 N / cm or more. B: The average peel strength is 6 N / cm or more and less than 8 N / cm. Δ: The average peel strength is 4 N / cm or more and less than 6 N / cm. Average peel strength is less than 4 N / cm

(7) Adhesiveness between insulating film and metal layer after accelerated test: Using sample (laminated body), accelerated test (HAST chamber EHS-221MD, 130 ° C., 85% RH, 100 hours, manufactured by Tabay Espec) Went. About the sample after an acceleration test, the peeling strength of an insulating film and a copper plating layer was measured based on JIS C6481-1996, and it determined by the following reference | standard based on the result.
A: The average peel strength is 8 N / cm or more. B: The average peel strength is 6 N / cm or more and less than 8 N / cm. Δ: The average peel strength is 4 N / cm or more and less than 6 N / cm. Average peel strength is less than 4 N / cm

(Synthesis example)
9-ethylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (hereinafter abbreviated as “ETCD”) 70 mol part, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid anhydride (hereinafter “ 30 mol parts (abbreviated as “NDCA”), 1.1 mol parts of 1-hexene, 540 mol parts of xylene and 4-acetoxybenzylidene (dichloro) (4,5-dibromo-1,3-dimesityl-4) as a ruthenium-based polymerization catalyst -Imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium (manufactured by Wako Pure Chemical Industries, Ltd.), 0.009 part, was charged into a pressure-resistant glass reactor substituted with nitrogen, and a polymerization reaction was performed at 80 ° C. for 2 hours with stirring. A solution of the ring-opening polymer was obtained. Next, 100 parts of the obtained ring-opening polymer solution was charged into an autoclave equipped with a stirrer that was purged with nitrogen, and the mixture was stirred at 150 ° C. and a hydrogen pressure of 7 MPa for 5 hours to conduct a hydrogenation reaction. A solution of 1) was obtained. The obtained polymer hydrogenated product (1) had a weight average molecular weight of 63,000, a number average molecular weight of 28,000, and a molecular weight distribution of 2.3. The hydrogenation rate was 99.9%, and the carboxylic acid anhydride group content was 30 mol%. The solid content concentration of the polymer hydrogenated product (1) solution was 25%.

[Example 1]
400 parts of the polymer hydrogenated product (1) obtained in Synthesis Example 1 (100 parts as the amount of the polymer hydrogenated product), hydrogenated bisphenol A diglycidyl ether (trade name YX8000, Japan Epoxy Resin Co., Ltd.) as the curing agent 36 parts), 1 part 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol as UV absorber, 1,3,5 as anti-aging agent 1 part of tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6-trione, 1-benzyl-2-phenylimidazole as curing accelerator 0.5 parts and 10 parts of liquid polybutadiene (trade name Ricon 152, manufactured by Sartomer Japan) as a component for improving flexibility, the solid content concentration is 30% In so that, to obtain a varnish of a curable resin composition by mixing xylene using a planetary stirrer. The film was coated on a polyethylene naphthalate film (support) having a size of 300 mm in length and 300 mm in width, a thickness of 100 μm, and a surface average roughness Ra of 0.08 μm, using a YD type doctor blade. Subsequently, it was made to dry at 80 degreeC for 10 minute (s) under nitrogen atmosphere, and the film with a support body whose thickness of curable resin composition was 30 micrometers was obtained.

  On the other hand, on the surface of the core material obtained by impregnating glass fiber with a varnish containing a glass filler and a halogen-free epoxy resin, copper having a thickness of 18 μm was stuck, thickness 0.8 mm, length 150 mm × The surface of a double-sided copper-clad substrate having a width of 150 mm was subjected to microetching treatment using an organic acid to obtain an inner layer substrate having a conductor layer on the surface.

  The two films with the support obtained above are cut into a size of 150 mm in length and 150 mm in width together with the support, and these films are placed on the substrate so that the curable resin composition of the film and the substrate are in direct contact with each other. On both sides. This was depressurized to 200 Pa using a vacuum laminator provided with heat-resistant rubber press plates at the top and bottom, and thermocompression bonded at a temperature of 105 ° C. and a pressure of 0.9 MPa for 60 seconds. Next, the support is peeled off, and the substrate with the curable resin composition is allowed to stand at 160 ° C. for 30 minutes in a nitrogen atmosphere, the layer of the curable resin composition is cured to form an insulating film, and a laminate of the inner substrate and the insulating film Got.

  The surface of the insulating film of this laminate was subjected to corona treatment with a batch corona treatment machine (CORONA GENERATOR CT-0212 manufactured by Kasuga Denki) under the conditions of an output of 0.75 kW, a conveyance speed of 1 m / min, a discharge gap of 3 mm, and a treatment frequency of 2 times. . Next, the distance from the mercury lamp to the laminate was set to 5 cm using a small ultraviolet surface treatment apparatus (SEN Special Light Source UVE200J, main wavelength: 253.7 nm, subwavelength: 184.9 nm) equipped with a high-output low-pressure mercury lamp. The surface of the adjusted and corona-treated insulating film was irradiated with ultraviolet rays for 5 minutes. When the surface roughness Ra of the insulating film of this laminate was measured, it was 0.07 μm.

  Subsequently, this laminate was immersed in an alkaline degreasing aqueous solution at 45 ° C. adjusted so that NaOH became 50 g / L for 2 minutes. Further, the laminate was then immersed in a water tank for 1 minute and further washed in water by immersion in another water tank for 1 minute, and then a conditioning agent (trade name CC-231, manufactured by Rohm & Haas) was added. It was immersed in the solution adjusted so that it might become 100 ml / L at 45 degreeC for 1 minute. Thereafter, the laminate was immersed in a water tank for 1 minute and further washed in a water tank for 1 minute, and then washed in an aqueous solution adjusted to have a palladium chloride concentration of 0.3 g / L at 45 ° C. Soaked for 2 minutes. Next, the laminate was immersed in a water bath for 1 minute and further washed in water by further immersion in another water bath for 1 minute, and then the aqueous solution adjusted so that sodium hypophosphite was 0.27 mol / L. Immersion was performed at 60 ° C. for 30 seconds to reduce the plating catalyst. Thus, the plating catalyst was made to adsorb | suck to the insulating film surface, and the laminated body which performed the plating pretreatment was obtained.

  Then, the laminate subjected to the plating pretreatment was 0.016 mol / L for copper sulfate pentahydrate, 0.0048 mol / L for nickel sulfate hexahydrate, and 0.052 mol for trisodium citrate dihydrate. / L, immersed in an aqueous solution adjusted to 0.5 mol / L boric acid, 0.27 mol / L sodium hypophosphite, and 1 g / L polyethylene glycol (molecular weight 1000) at 45 ° C. for 5 minutes. By performing electroless plating, a metal layer (copper layer) was formed on the insulating film.

  Then, the electroless-plated laminate was obtained by using copper sulfate 100 g / liter, sulfuric acid 50 g / liter, 36% hydrochloric acid 1.4 ml / liter, EVF-1A (manufactured by Uemura Kogyo Co., Ltd.) 1 ml / liter, EVF-B (Uemura (Manufactured by Kogyo Co., Ltd.) 10 ml / liter, EVF-R (manufactured by Uemura Kogyo Co., Ltd.) 2 ml / liter of an aqueous solution (electrolyte solution) adjusted to be 2 ml / liter, while blowing air to the temperature of 23 ° C. A copper plate was immersed and placed on the anode side, energized with a direct current power supply device, subjected to electrolytic copper plating, and an electrolytic copper plating film having a thickness of 12 μm was formed on the metal layer formed by electroless plating. Next, the laminate subjected to electrolytic plating was annealed at 170 ° C. for 60 minutes to obtain a laminate having a metal layer formed by plating on the outermost side. The obtained laminated body was used for the test for evaluating the adhesiveness of an insulating film and a metal layer. The results are shown in Table 1.

[Example 2]
Instead of corona treatment, an atmospheric pressure plasma treatment apparatus (ADMASTER II-300dM: manufactured by E-Square) outputs 1.8 kW, nitrogen flow rate 200 L / min, clean dry air flow rate 200 L / min, conveyance speed 0.5 m / min, A laminate of Example 2 was obtained in the same manner as in Example 1 except that the plasma treatment was performed under the condition of one treatment. This was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3
A laminate of Example 3 was obtained in the same manner as Example 1 except that liquid polybutadiene was not blended. This was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
Fluorine having a size of 250 mm x 250 mm and a thickness of 9 μm on a polyethylene naphthalate film (support) having a size of 300 mm x 300 mm and a thickness of 100 μm and an average surface roughness Ra of 0.08 μm. Then, the varnish obtained in Example 1 was applied to the fluorinated aramid film using a YD type doctor blade (gap size 130 μm). Next, the first curable resin composition layer was formed by drying the fluorinated aramid film coated with the varnish for 10 minutes at 80 ° C. in a nitrogen atmosphere. The support is peeled off from the laminate of the obtained fluorinated polyamide film and the curable resin composition layer, and varnish is applied to the surface opposite to the previous coating surface of the film with the first outer layer in the same manner. By drying under the same conditions, a layer of the second curable resin composition is formed, and the support (polyethylene naphthalate film) / the second curable resin composition layer / fluorinated aramid film ( Substrate) / first curable resin composition layer was laminated in this order to obtain a film with a support of Example 4. The thickness of each of the first curable resin composition layer and the second curable resin composition layer with the support was 10 μm.

  The laminate of Example 4 was prepared in the same manner as in Example 1 except that the film with a support of Example 4 produced by the above method was used instead of the film with a support of Example 1. Obtained. This was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 5
A laminate of Example 5 was obtained in the same manner as Example 1 except that the liquid polybutadiene was not mixed and the corona treatment was not performed. This was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
A laminate of Comparative Example 1 was obtained in the same manner as Example 1 except that the ultraviolet irradiation treatment was not performed. This was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
21 parts of liquid bisphenol F type epoxy resin (trade name “JER807”, manufactured by Japan Epoxy Resin Co., Ltd.), 13 parts of naphthalene type tetrafunctional epoxy resin (EXA-4700, manufactured by Dainippon Ink & Chemicals, Inc.), methyl ethyl ketone 10 And 10 parts of cyclohexanone were stirred using a planetary stirrer and dissolved by heating. 26 parts of methyl ethyl ketone varnish (trade name “Phenolite LA-7050”, manufactured by DIC Corporation) and 20 parts of phenoxy resin varnish (trade name “FX293”, manufactured by Tohto Kasei Co., Ltd.) are added. By doing so, a varnish was obtained. About the subsequent operation, the laminated body of the comparative example 2 was obtained like Example 1 except having used this varnish. This was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  As is apparent from Table 1, the surface of the insulating film obtained by curing the alicyclic olefin polymer having a functional group is irradiated with ultraviolet rays, and then the surface of the insulating film irradiated with the ultraviolet rays is electrolessly plated. When the metal layer is formed by the method, it can be said that a circuit board having excellent adhesion between the insulating film and the metal layer can be obtained (Examples 1 to 5). In particular, when an insulating film that has been dry-processed (corona-treated or plasma-treated) before being irradiated with ultraviolet light is used, a circuit board having excellent adhesion between the insulating film and the metal layer can be obtained even after the acceleration test. (Examples 1-4). On the other hand, even when an insulating film obtained by curing an alicyclic olefin polymer having a functional group is used, if the surface is not irradiated with ultraviolet light, the adhesion between the insulating film and the metal layer (Comparative Example 1). In addition, when a curable resin composition for forming an insulating film containing a polymer other than an alicyclic olefin polymer having a functional group is used, the insulating film and the metal are not irradiated with ultraviolet rays. The adhesion with the layer was poor (Comparative Example 2).

Claims (3)

  The surface of the insulating film formed by curing the curable resin composition containing the alicyclic olefin polymer having a functional group and the curing agent was irradiated with ultraviolet rays, and then the ultraviolet rays were irradiated. A method for manufacturing a circuit board, comprising a step of forming a metal layer on a surface of an insulating film by an electroless plating method.   The method for manufacturing a circuit board according to claim 1, wherein the surface of the insulating film is subjected to a dry process treatment before the surface is irradiated with ultraviolet rays.   The method for manufacturing a circuit board according to claim 2, wherein the dry process treatment is plasma treatment or corona treatment.